JPS59116120A - Ferrosilicate molecular sieve composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to crystalline ferrosilicate compositions exhibiting adsorption, ion exchange and catalytic properties. This new group of ferrosilicates of the invention is herein referred to as Fe5Q-3
Collectively referred to as 5.

BACKGROUND OF THE INVENTION Ferrosilicates, which have a three-dimensional crystal structure consisting of S+O2 and FeQ2'' tetrahedrons, have been described in the past in U.S. Pat. and European Published Patent Publication No. 0, Oi 3.63 of M.K. Lupine et al.
No. 0 (U.S. Patent Application No. 003 filed January 15, 1979)
．． No. 144, which claimed priority rights). The latter document concerns the production of silicates containing iron and/or chromium and which may optionally contain aluminum. These silicates are said to be a new type of zeolite ZSM-12.

The former document is generally described, but the two types characterized by their X-ray powder diffraction patterns appear to have a close structural relationship with the zeolite ZSM-5 and the zeolite mineral ferrierite, respectively. It is. In both cases, the composition must contain an organic templating agent and may be hydrothermally extracted from an aqueous reaction mixture which may contain an alkali metal or alkaline earth metal cation as a component. It is synthesized.

Ferrosilicate (Fe50-
3 a) on October 12, 1982.
No. 433.909, filed on May 1, 2009. The ferrosilicate of U.S. Patent Application No. 433,909 is characterized by the following X-ray diffraction pattern.

6.4-6.65 13.8-13.3M-VS
9.7-9.85 9.12-8.98 8
-VS13.4-156 6.61-S, 51
M-822, 2-22, 454, 00-598
M-825, 55-25, 83, 486-3, 45
58-V52765-2'lB5 3.22+5-
5203 M-8 SUMMARY OF THE INVENTION The present invention is directed to microporous crystalline ferrosilicate compositions having uniform pore sizes greater than about 4.0 pore size and less than about 5 pore size. This empirical formula, expressed in terms of oxide molar ratios in the anhydrous state, is: 3M2/nO:[AlxFe(1-x)]203:bS
iO2 [in the above formula, "M" is at least one cation having a valence "n II, II a W has a value of 0 to 2.0, and bl' has a value of 5 to 100; , and wxl' has a value of 0 to 0.98], and the 7 erosilicate has a characteristic X# powder diffraction pattern that includes at least the d-spacings of Table I below.

DETAILED DESCRIPTION The present invention provides a uniform pore size greater than about 4.0 and less than about 5, expressed in anhydrous oxide molar ratio 3M2/nO:[AIxFe(,-x)]203: bS
i02 [In the above formula, "M" is at least one cation having a valence of 1 n n, and "alt is 0 to 2
．． II bI+ has a value of 5 to 100 and xl' has a value of 0 to 098] and a characteristic X comprising at least the d-spacing of Table I below. The present invention relates to a new class of microporous crystalline Fetetrasilicates having a linear powder diffraction pattern.

Table I 2θ d(A) Relative intensity 10.9
-11.1 8.12-7.97 M-
VS13.4-13.5 6.61-6.56
M-817, 4-17, 55, 10-5, 07
M-8210-2114, 23-4, 21M-822,
0-22,14,04-4,02M-V S28,J
3.121 M-832,
3-52,42,772-2,7 (53M-8) The composition of this 7 erosilicate was determined by the experiment described above.
Preferably, it has a value of 0 to 80 and l1x11 has a value of θ to 0.5. Most preferably al' has a value between 0 and 1,0 and 1+b1 is 10
~50, and llX″ is essentially ze4 or 0
Less than 01.

All of the Fe5O-35 compositions analyzed to date are
It was further characterized by the X-ray diffraction pattern in Table ■.

Table ■ sh-Shoulder The X-ray diffraction patterns in Tables T and ■ and all other X-ray diffraction patterns described below were obtained using standard X-ray powder diffraction techniques. The irradiation source was a high-strength steel target and the X-ray tube was operated at 50 Kv and 40 ma. Diffraction patterns from the MK irradiation and graphite monochromator are suitably recorded by an X@spectrometer scintillation counter, pulsed hide analyzer and strip chart recorder. The flat compacted powder sample is scanned at 2° (2θ) in 7 minutes using a time constant of 2 seconds. The interplanar spacing +d> is obtained from the position of the diffraction peak represented by 20 (θ is the Black angle) when observed on a strip chart.

Intensity is determined from the height of the diffraction peaks after background subtraction. The strength of the strongest line is I. Binding,
The relative intensity value is determined by substituting this into the formula "1o x I/I." (where ■ is the intensity of each line other than the strongest line).

In some cases, the numerical value obtained using the formula is the symbol vs.
Reported in %S%m%W and vw (which stand for very strong, strong, medium, weak and very weak, respectively).

As will be appreciated by those skilled in the art, the measurement of parameter 20 is subject to both human and machine error, thus imposing an error margin of approximately ±0.4 on each reported 2θ value. I can do it. Of course, this uncertainty also appears in the reported value of d-distance in λ calculated from the 2θ values.

However, this uncertainty is common in the art and is not sufficient to prevent the crystalline materials of the present invention from being distinguished from each other and from prior art compositions.

The Fe5O-35m paraboloid of the present invention is SiOFed2″″
2% and optionally a three-dimensional network of A102-tetrahedrons. In the as-synthesized form, electrical neutrality is provided by charge-balancing cations associated with the F e 02- and Al02- tetrahedra in the framework structure.

Alkali metals, alkaline earth metals, and organic cations derived from organic templating agents can all be present in the as-synthesized form of Fe50-35, but this is due to their presence in the synthesis reaction mixture. This is achieved by Alternatively, the organic template compound can simply be absorbed into the pores of the crystal structure, ie, can exist as an adsorbed or encapsulated phase without being bound to the crystal lattice. It is possible for both types of organic components to be present within the same structure. The maximum amount of organic species present depends on the molecular size of the shelled molecule or ion and its morphology. The cation derived from the organic template agent is Fe5O-3
Such organic cations are considered to be ion-exchangeable in the usual sense if they have a dynamic diameter larger than the effective pore size of 5, i.e., if they occupy lattice positions that cannot be sharpened when approaching wide pores. Not done. However, such cations can be thermally decomposed to form ion-exchangeable ammonium or hydrogen cations, usually by calcination in air at temperatures of 200-700°C. Most of the non-organic cations become ion-exchangeable after access to the internal structure of the Fe5O-35 crystal is achieved by substantial removal of pore-clogging organic species and thus other metal cations as well as NI (Can be replaced by 4+ and TT+ cations. Conventional ion exchange operations are applicable. Activation, or dehydration, to remove adsorbed water from the crystals can be performed at Although easily accomplished, calcination in air at elevated temperatures up to 700° C. is generally convenient and preferred for this reason.Fe5O-35811 compositions are generally
It is calcined at a temperature ranging from 50° C. to the crystal decomposition temperature of the ferrosilicate.

templating agent
) influences the crystallization mechanism is not yet well known, but the size and shape of the molecule appear to be important factors. Methylquinuclidine has been found to work well as a templating agent for the formation of Fe5Q-35 materials, and these are preferred in the present invention. For this purpose, at least one element of group VA of the Periodic Table of the Elements (N, P, As, Sb and Bl) containing preferably nitrogen or phosphorus and having from 1 to 7 carbon atoms is used. Other organic (including organometallic) compounds from the group containing alkyl or aryl groups are also suitable. Quaternary ammonium compounds and amines can also be used in the present invention. Mixtures of suitable templating agents are also useful in preparing Fe5O-s5 compositions.

Fe5O-35 is expressed in molar ratio of oxides within the following range: 0 to 10R202 1 to 15 M2/rIO: [AI
XFe(1-x)1203:10-20O5in2:
200-1. OOOH2O [in the above formula, '1R11
represents an organic templating agent, preferably an alkylquinuclidine, an amine or a quaternary ammonium compound;
I' represents an alkali or alkaline earth metal having a valence l+n''.

and lIX'' has a value of 0 to 0.98.

Preferably, the molar ratio of oxides in the reaction mixture is between 1 and 5.
R20: 4-12M2/. 0: CA, 1xFe(1
-x)]203:20~5osio2:400~<
5OOT-T, 0 [in the above formula, "M" represents one or a mixture of two or more of sodium, potassium, and calcium]. More preferably, the reaction mixture is 1-5R20:4-10M2/nO:[AIxFe(1
-x)]203:20~80Si02:400~60
It consists of a composition of 0H20. Most preferably, the reaction mixture does not contain any aluminum other than the aluminum that may be present as an impurity in the reactants providing other oxide components (in which case II
with a value of ~0.5).

However, it is also possible to promote crystallization by adding seed crystals with lewynite crystal structure to the reaction mixture.
It will be appreciated that although e5Q-35 can be formed, such seeding methods are part of the preferred synthetic procedure. Of course, the use of pre-prepared Fe5Q-35 compositions as seeds can greatly reduce the amount of aluminum imparted to the reaction mixture as a result of such seeding operations. Fe5 by the use of seed crystals
When preparing O-35, the seed crystals are preferably at least 1% and more preferably at least 0% based on the solid oxide weight of the other components in the reaction mixture.
Used in 1% to 10% of rats.

In preparing the reaction mixture for IM, conventional reactants used in zeolite synthesis are generally suitably used. Iron is FeC1, Fe(No), vinegar 5
3 5 Iron acid, iron hydroxide, iron acid) It can be given as a salt such as IJum. Sources of silica include reactive forms of amorphous silica, such as silica gel, precipitated silica, fumed silica, silica sols, and silica aerogels, as well as alkali metal silicates. If aluminum is intentionally added, it may be in the form of alpha-alumina, gamma-alumina, sodium aluminate, aluminum alkoxide, alumina trihydrate, boehmite, and the like. The alkali metals and/or alkaline earth metals are preferably added as hydroxides, but water-soluble salts of the metals can also be used. The organic template agent H has been explained previously.

The reaction was carried out under static or stirred conditions in a sealed reactor for 10 min.
It can be carried out at temperatures in the range from 0 to 250°C and under natural pressure. The reactor is preferably lined with an inert plastic material MS+ such as polytetrafluoroethylene.

Although not clearly proven, Fe5Q-'55
is considered to be structurally related to the mineral zeolite levinite, even though the chemical composition differs in structure due to the presence of the tetrahedral F e Q structural unit.

This composition has been found to have hydrophilic adsorption properties and exhibits substantial acidity of the type useful for catalytic conversion of hydrocarbons. It is therefore useful both as an adsorbent and as a catalyst or catalyst substrate in the same applications that have traditionally used zeolites in general and small pore zeolites in particular.

Example 1 1a) 1s, qg of iron nitrate hydrate (Fe (No3)
3.9H,,Q) with 50.4 g of aqueous methylquinuclidine (MeQ) (49-iteXMeQ) and 95.3.9
A reaction mixture was prepared by combining 6 Ludox LS'' aqueous silica sol (5Gi 4% by weight 5I02).

This mixture was mixed thoroughly. Add itog to this mixture.
A further solution of 24.9 g of sodium hydroxide (NaOH) in water was added and the mixture was stirred until homogeneous. The composition of the final reaction mixture expressed in oxide molar ratio is: 5.0 (MeQ) 20 : Fe, 03: 27
．． 65ho2: 8.0Na20: 400 FT20
(Although here the template agent is shown, it may also be shown in the following examples as a cation or as a related cation in oxide form. Thus, the formula (MeQ) 20 , MeQ corresponds to the methylquinuclidine cation).

The reaction mixture was placed in a stainless steel pressure vessel lined with an inert plastic material (polytetrafluoroethylene) and heated at 200° C. under natural pressure in a furnace for 4 hours.
Heated for 6.0 hours. The solid reaction product was collected by centrifugation, washed with water and dried in air at 100°C.

(bl) A portion of the solid product from (a) above was analyzed by X-ray analysis. The product had an X-ray powder diffraction pattern characterized by the following data:
I/Io is the relative intensity and IIdll is the interplanar spacing.

Table A: Impurities from other species Long ago May contain impurities from other species (C)
A portion of the product of the above (bl) was heated to about 550 mL in air.
Calcined at °C for 325 hours. The calcined product had an X-ray powder diffraction pattern characterized by the following data.

Table 1 B: Impurities from other species ++ fdl that may contain impurities from other species
Adsorption capacity was measured for the tc+ calcined product using a standard Mackbain-Baker heavy-duty adsorption apparatus. The following data were obtained for the sample activated at 350°C.

02! L46 10B-1830602",
, 46 730 -183 12.5T (,,
02,654,624B,D H202,6519,52512,7 jl-%xane 4.3'102
24! The pore size of the L5 calcined raw material is greater than about 4.5, as shown by the adsorption of n-hexane with a dynamic diameter of 4.3.

Example-2- (ali6.2g of iron nitrate hydrate (F'e (No3)
5-9 H2O') and 571 g of aqueous methylquinuclidine (25% MeQ) and 11 [1,5,! i+
A reaction mixture was prepared by combining and thoroughly mixing with an aqueous silica sol (30 wt% 5i02). To the resulting mixture was added 12.8 g of sodium hydroxide (
15.9.9 of NaOH) dissolved in water was added and the mixture was stirred until a homogeneous mixture was obtained. The composition of the final homogeneous reaction mixture in terms of oxide molar ratios is: 2.5(MeQ)20:Fe2O3:2Z6SIO2:
It was 8.0Na20:800H20. The reaction mixture was placed in a stainless steel pressure vessel lined with an inert plastic material (polytetrafluoroethylene) and heated in an oven at 150° C. under natural pressure for 24 hours. The solid reaction product was collected by centrifugation, washed with water and dried in air at 100°C. The main component of the solid had an X-ray diffraction pattern characterized by the following data.

Table C 52,52,7725N 34.62.592N 55.6 t653
5sh = shoulder [b] Chemical analysis of the above fat product gave the following chemical composition.

Wt6% Carbon 103 a2021 Fe20. 10.8 Sin265.1 LOI 23.0 This is expressed as oxide molar ratio [1,51NazO: Fe2O3: 16.255t
o2: gave a product composition of 0.80 (MeQ)20.

A portion of the product of (cJ fb) above was calcined in air at 550°C for 2 hours. When this product was analyzed by X-ray, it had an X-ray powder figure characterized by the data on the table.

Table D 2θ d(A) 100 I/TOfd
+ The adsorption capacity was measured on the calcined raw material of (Cl) using a standard McPayne-Baker IT adsorption apparatus. The following data were obtained for the sample activated at 350°C.

02"r, 46 100 -185 18.60
2146 754 -185 21.5H20
2,654,624117 IT20 2.65 1B, 5 24
17.4n-hexane 4. '；98
24 9.4 Inbutane 5.0
From the 755 24 0.2-F data, the pore size is greater than about 4.3, as shown by the adsorption of n-hexane, and about 5.0, as shown by the negligible adsorption of isobutane. was measured to be smaller than

Example 3 (N15.4.iil iron nitrate nine hydrate, 19.0 g
of methylquinuclidine (25 wt% MeQ) and 3&
8 g of aqueous silica sol (30 wt. x SIO,) -
Fe5O-55 was prepared by combining This mixture was stirred until a homogeneous mixture was obtained. to this,
4.2g of sodium hydroxide and 0.39g of sodium aluminate (Na20-Al2O3.3H20) were added to 17
．． A solution of 5 g dissolved in water was mixed. This mixture was stirred until a homogeneous mixture was obtained. The composition of the reaction mixture expressed in terms of oxide molar ratio is 2.5 (Me
Q) 20: Fe2O3: 0.2Al 203:
27/iS 102: 8.0Na20: 5 ooH
It was 20.

The reaction mixture was placed in a stainless steel pressure vessel lined with an inert plastic material (polytetrafluoroethylene) and heated in an oven at 150° C. under natural pressure for 94 hours. solid reaction products are recovered by centrifugation;
It was washed with water and dried in air at 100°C. A portion of the product was analyzed chemically and by X-ray analysis to reveal Fe5, which corresponds to the X-ray diffraction pattern shown in Table 1 above.
It was found to be characterized as O-35.

(bl Chemical analysis of the product shows that 9.5% by weight carbon,
40% by weight Na2O, t2 heavy rough blade Al2O3,95
It showed wt% Fe 20x, 6n9 wt% SiO2 and 24.3 wt% LOI. This is expressed as an oxide molar ratio of 0.81 Na 20 : 0.19A-' 205
: Fe2O3: 17.5S 102: 0.82
A product composition of (MeQ) 20 was given.

(cl) A portion of the product of (a) above was calcined in air at about 600°C for 2 hours.
When analyzed by rays, it had an X-ray diffraction pattern characterized by the data in the table above.

fdl The adsorption capacity of the calcined sample (C) above was measured using a standard McPayne-Baker M adsorption device. The following data were obtained for the sample activated at 350°C.

02 546 100 -183 15
．． 2023.46754 -183 18. IH,,
02,654,6249,9 H202,65,1B, 5 24 15.6n-
Hexano 4.5 98 24
8. Fiisobutane 5.0 755
24 0.6 From the above data, when measuring the pore size of Fe5Q-35, it is larger than about 4.3 and about 5
It was smaller than 0 people.

Examples 4-12 In each of Examples 4-12, the following oxide molar ratios, aNa20
:b(MeQ)20:CFe2O3:dSiO2:eH
A reaction mixture was prepared in the manner of Example 2 using a reaction mixture corresponding to No. 20. a, b, c, d and e on each side
The values were as follows.

4 8.0 5.0 1. o 276400 200
2345 B, 0 2.5 1,0 27.6
400 200 646 B, 0 2.5 1,
0 50.0600 200 647 80 t
251. o 27.6400 150 20B8
B, Ot25to 27.6400 200
459 B, 0 2.5 10 2G, 0500
150 59610 B, 0 2.5 to
20.0500 200 4511 B, 0
2.5 10 80.0800 200 4512
4.0 2.5 1.0 27.6500 150
It can be seen that Fe5Q-35 was produced in each case as evidenced by 596 X-ray analysis.

Examples 13 and 14 In Examples 13 and 14, to illustrate the catalytic activity of Fe5O-35, Fe
Calcined samples from the 5O-35 composition were prepared. However, in Example 13, the reaction mixture was heated at 150° C. for 232 hours.

The Fe5Q-3511J composition was then tested for catalytic cracking. The test procedure used was that 5 g (20-40 mesh) of Fe5 were tested with a 2 mole nine' helium flow of n-butane in a quartz tube reactor with an outside diameter of 1.4 in.
It was a catalytic cracking with premixing on the O-35 sample. The samples were activated in situ at 500° C. for 60 minutes under a dry helium barge at 200 F3/min. 2 mole % n-butane in helium was then passed over the sample for 40 minutes at a flow rate of 50 am'/min, and product stream analysis was performed at 10 minute intervals. Then, the catalytic activity of Fe5Q-35 was investigated by calculating the pseudo-order rate constant (KA). two F's
The KA value (crr
L3/gmin) are 3.7 and t2, respectively, indicating that Fe5O-35 is catalytically active for the conversion of organic feedstocks.

Claims (1)

[Claims] m Expressed by oxide molar ratio in anhydrous state a M
27nO: (A, 1xFe(+-x)]
20s: b S + 02 [In the above formula, "M" is at least one cation having a valence of 1 Inl', "a lt has a value of 0 to zOO, and b" has a value of 3 to 1
00 and Itx" has a value of 0 to 0.98], and has a characteristic crystalline ferrosilicate composition. (The value of 2+"a" is 0 to to, and the value of +b!+ is 1.
0 to 80, and the value of X'' is 0 to 0.5. (3) The value of It a I is O to i, O''C-;
The composition according to claim 2, wherein the value of +bl' is 10 to 50 and the value of X'' is substantially 0. (4) The composition according to claim 1 is heated at 350°C. Microporous crystalline ferrosilicate produced by calcination at a temperature within the range from 350° C. to the crystal breakdown temperature of 7 erosilicate. Microporous crystalline ferrosilicate produced by calcining the composition according to claim 3 at a temperature ranging from 350° C. to the crystal breakdown temperature of the ferrosilicate. Microporous crystalline ferrosilicate prepared by calcination at a temperature in the range of (7) 0-10R20:1-15M27,0: [AlxF
e(1-x))205:10~200Si02:2
00-1. OOOH2O [In the above formula, M is the valence ++
an alkali metal or alkaline earth metal cation with nw, R is an organic templating agent, and llX
17 and maintaining this mixture under natural flow at a temperature of 100 to 250 °C until crystals of ferrosilicate are formed. Claim 1
Method for producing ferrosilicate as described in Section 1. (8) ++MI+ is one of sodium and potassium
represents a species or mixture and the oxide molar ratio is 1 to 5R
20:4-10M2/. Q: (AlxFe (1-
x) 120s: 20~80SiO°400~600
H,,02. 8. The method of claim 7, wherein XI+ has a value of 0 to 0.5. (q) The method according to claim 7, wherein the value of II x * is 0. 8. The method of claim 7, wherein the source of Fe2O3 is iron nitrate.